Systems, Devices, and/or Methods for Managing Batteries

ABSTRACT

Certain exemplary embodiments can provide a system, which can comprise an ultra-thin polymer ceramic composite separator. The ultra-thin polymer ceramic composite separator can comprise Li-ion conducting ceramic material. The ceramic composite separator has a columnar grained microstructure. The ultra-thin polymer ceramic composite separator can comprise a single or bi-layer combination of LiPON, LATP, garnets, lithium sulfides, or Li 1+2x Zr 2−z Ca(PO 4 ) 3 .

CROSS-REFERENCES TO RELATED APPLICATIONS

This application claims priority to, and incorporates by referenceherein in its entirety, pending U.S. Provisional Patent Application Ser.No. 62/324,261 (Attorney Docket No. 1099-04), filed Apr. 18, 2016.

BRIEF DESCRIPTION OF THE DRAWINGS

The patent or application file contains at least one drawing executed incolor. Copies of this patent or patent application publication withcolor drawing(s) will be provided by the Office upon request and paymentof the necessary fee. A wide variety of potential practical and usefulembodiments will be more readily understood through the followingdetailed description of certain exemplary embodiments, with reference tothe accompanying exemplary drawings in which:

FIG. 1 is executed in color. FIG. 1 shows A) Bi-layer LiPON/LATPdeposition process. B) UTCPP Separator in transportable form and C) infinal form;

FIG. 2 is a table;

FIG. 3 is a schematic representation of a system 3000; and

FIG. 4 is a flowchart of an exemplary embodiment of a method 4000.

DETAILED DESCRIPTION

Certain exemplary embodiments can provide a system, which can comprisean ultra-thin polymer ceramic composite separator. The ultra-thinpolymer ceramic composite separator can comprise Li-ion conductingceramic material. The ceramic composite separator has a columnar grainedmicrostructure. The ultra-thin polymer ceramic composite separator cancomprise a single or bi-layer combination of LiPON, LATP, garnets,lithium sulfides, or Li_(1+2x)Zr_(2−z)Ca(PO₄)₃.

The use of metallic lithium anodes is desired for advanced Li-basedbatteries (Li-ion, Li—S, Li-Air) to enable higher energy density andspecific capacity. Unfortunately, when utilizing Li metal anodes,lithium dendrite growth during recharging can result in extremeroughening of the lithium surface, which can short circuit the batterycell. Mechanical suppression of the dendrite formation through the useof high shear modulus, Li-ion conducting materials is a promisingapproach to avoid the roughening issue and enable lithium metal anodesas Li-ion conducting ceramics have been developed with conductivitiesapproaching that of liquid electrolytes. However, poor mechanicalproperties of the Li-ion conducting ceramics can be a significantchallenge when manufacturing thin layers due to their poor toughness andsensitivity to defects. This has led to the use of polymer-ceramiccomposite separators having enhanced mechanical performance. Certainexemplary embodiments manufacture ultra-thin polymer ceramic composite(“UTPCC”) separators having a low ionic area-specific resistance,suitable mechanical properties and good compatibility in contact withlithium metal. Certain exemplary embodiments provide the manufacture ofthese separators in a cost effective manner via the use of a high rate,gas-jet assisted vapor deposition process that operates in a soft vacuum(approximately 10 Pa) to enable continuous roll-to-roll manufacturingonto flexible substrates. Using this manufacturing technique, UTPCCseparators having thicknesses less than approximately 20 micrometers canbe created.

Certain exemplary embodiments provide for a substantially continuousmanufacture of UTPCC separator material meeting the specifications toallow the use of Li metal negative electrodes in multiple batteryplatforms (i.e. Li-ion, Li—S, Li-Air). The separators can comprise abi-layer of high modulus, Li-ion conducting ceramic materials (e.g., abi-layer comprising LiPON and LATP) having a columnar grainedmicrostructure. A non-lithium ion conducting polymer (e.g.,cyclo-olefin) can be infiltrated into the columnar pores to result in apolymer-ceramic composite membrane. The manufacture of these separatorscan utilize a relatively high rate, gas-jet assisted vapor depositionprocess that operates in a soft vacuum (approximately 10 Pa) to enablesubstantially continuous roll-to-roll manufacturing onto flexiblesubstrates using a unique atmosphere to vacuum (“ATV”) technology.

Certain exemplary embodiments provide for safe, stable batteries havinghigh energy and power density, long cycle lives and large operationaltemperature ranges are required in multiple applications. Li-basedbatteries can provide increased energy density over other batteries.Advanced manufacturing techniques can be utilized to develop Li-basedbatteries that are affordable to manufacture, long lived, safe, anddeliver the high energy density values predicted theoretically. One areathat has the potential to significantly enhance the performance ofLi-based batteries (Li-ion, Li—S, Li-Air) is the use of metallic lithiumanodes due to its ability to enable higher energy density and specificcapacity. Unfortunately, lithium dendrite growth during recharging canresult in extreme roughening of the lithium surface that can shortcircuit the battery cell. Mechanical suppression of the dendriteformation through the use of high shear modulus materials is a promisingapproach to avoid the roughening issue and enable lithium metal anodes.The suppression of dendrite formation can be achieved using materialshaving a shear modulus approximately twice that of Li metal. Thisgenerally excludes the use of organic Li-ion conducting membranes andrequires ceramic or glass materials with higher shear moduli. Thedevelopment of Li-ion conducting ceramics and glasses withconductivities approaching that of liquid electrolytes have made solidLi-ion conducting materials a viable approach for dendrite suppression.However, the manufacture of Li-ion conducting separators based on suchmaterials can be limited by several factors:

-   -   the higher than desired ionic area-specific resistance (“ASR”)        of these components;    -   the electro/chemical stability of these materials when in        contact with Li metal and air; and/or    -   relatively poor mechanical properties of the thin ceramic/glass        separators (i.e., low toughness).

The high ASR of current separator materials is a function of the higherthan desired thickness (approximately 100 to approximately 250 microns)and the presence of high impedance grain boundaries and/orparticle-to-particle interfacial resistances that are the result ofconvention powder based manufacturing approaches (i.e. powder compactionand sintering; tape casting). These issues resulted in a motivation tocreate very thin separators (less than approximately 20 microns) withlimited grain boundary and interfacial resistance (i.e., substantiallysingle crystals). The poor mechanical properties of the Li-ionconducting ceramics is a significant challenge when manufacturing thinlayers due to their poor toughness and sensitivity to defects. This hasled to the use of polymer-ceramic composite separators. For example,composite separators using a single layer of particles can be embeddedin a polymer matrix. The approach uses a non Li-ion conducting polymer(e.g., cyclo-olefin) and approximately 100 micron diameter particles ofan ion-conducting ceramic (e.g., Li_(1.6)Al_(0.5)Ti_(0.95)Ta_(0.5)(PO₄)₃(LATTP)) to create durable, ion conducting layers. The non Li-ionconducting, organic matrix resists Li dendrite formation despite itsrelatively low shear modulus. The ASR of this material is, however,limited by the thickness, grain boundary resistance within the particlesand the relatively low volume fraction of the LATTP in the composite.The LATTP is also not stable in direct contact with Li metal. Certainexemplary embodiments can utilize this basic composite concept whileproviding disruptive advances in performance that overcome these currentdrawbacks.

In certain exemplary embodiments, UTPCC separators can be created fromthe vapor phase using a high rate, high throughput physical vapordeposition approach that uniquely operates in a soft vacuum to allow gasjet assisted deposition and substantially continuous ATV processing. Thegas jet assisted deposition allows for an enhanced deposition efficiency(and therefore very high deposition rates) and the utilization of athree dimensional coating zone (due to the non-line-of-sight coatingcapability of the process) for ultra-high coating throughout. The ATVtechnology allows substantially continuous roll-to-roll manufacturing.

Using this manufacturing technique, a bi-layered ceramic material(LiPON/LATP) having a columnar microstructure can be created. WhereLiPON is lithium phosphorous oxy-nitride and LATP isLi_(1+x)Al_(x)Ti_(2−x)P₃O₁₂. The columnar structure limits grainboundary resistance by aligning the boundaries in the direction ofLi-ion transport and maximizing the volume fraction of the Li-ionconducting material. The bi-layer structure enables direct contact ofthe separator to Li metal. Infiltration of a non Li-ion conductingpolymer into the columnar pores completes the composite structure. Theproposed product utilizes several key innovations to create a disruptiveproduct for the marketplace. These include:

-   -   1) Soft vacuum physical vapor deposition: Allowing substantially        continuous atmosphere-to-vacuum roll-to-roll processing and        non-line-of-sight physical vapor deposition.    -   2) High rate deposition of ceramic layers with columnar        microstructures over large areas: greater than approximately 10        microns/min over large areas (greater than approximately one m²)        appear feasible using moderately sized, affordable coaters.    -   3) 3D coating zone during physical vapor deposition: Enabled by        non-line of sight (“NLOS”) coating capability.    -   4) Porosity tailoring: Microstructures having grains elongated        in the desired Li-ion diffusion direction demonstrated for        zirconia structures, which can reduce grain boundary resistance.    -   5) Bi-layer separators: for enhanced Li metal compatibility.

The innovations of exemplary embodiments provide an opportunity toaffordably create very thin (approximately 5 to approximately 20microns) composite separators (ceramic/polymer) having microstructuresand architectures substantially optimized for Li-ion transport andelectro-chemical stability using roll-to-roll processing. Theanticipated metrics of the resulting separators are disclosed herein.

FIG. 2 is a table, which documents properties of an exemplary embodimentcompared to two other materials.

Certain exemplary embodiments provide a bi-layer ceramic comprising aninitial LiPON layer (e.g., first bi-layer 3200 of FIG. 3) followed by anLATP layer (e.g., second bi-layer 3300 of FIG. 3). LiPON can be chosenbased on its known compatibility with Li metal. This layer can be thinas its Li-ion conductivity is several orders of magnitude lower thanLATP. The LATP layer can be chosen for the majority of the bi-layer dueto its very high bulk Li-ion conductivity, good air stability andsuitability for high rate evaporation. Li garnets and Li sulfidematerials can also be considered. Li sulfides can also be considered forvapor deposition. Both single and bi-layer combinations of LiPON, LATP,garnets (examples include Li₇La₃Zr₂O₁₂) and Li sulfides (examplesinclude Li₁₀GeP₂S₁₂) may be considered for use in the separator.

The manufacture of the separator can utilize a production scale DirectedVapor Deposition (“DVD”) coater. The DVD technology can utilize asupersonic gas jet to direct and transport an electron beam evaporatedvapor cloud onto a component. Typical operating pressures are in therange of approximately 1 to approximately 50 Pa, which can utilize fastand inexpensive mechanical pumping such that chamber pump down times areshort. In this processing regime, collisions between the vapor atoms andthe gas jet create a mechanism for controlling vapor transport. Thisenables high rate deposition (by combining high evaporation rates withhigh deposition efficiency) and NLOS deposition that enables 3Dutilization of the coating zone to increase the surface area ofsubstrate that can be coated in a given time. Multi-sourceco-evaporation approaches can be utilized that allow the DVD coatingzone to be scaled from small area, tightly focused cylindrical fluxes tolarge area rectangular fluxes. When such fluxes are used with 3Dutilization (due to NLOS capabilities), the coating zone can easilyexceed approximately one (1) square meter using moderately sized,relatively inexpensive coating equipment. Importantly, the soft vacuumused in the process enables ATV processing for substantially continuousroll-to-roll manufacturing. A production scale, roll-to-roll, continuousfiber/wire/tape handling system has been built that has beendemonstrated for the application of functional coatings onto longlengths of continuous substrates (greater than approximately 2000 feet).Production scale DVD equipment can be used to manufacture UTPCCseparators. This can comprise first depositing NaCl onto a metal foil.This can be followed by an in-situ deposition of a LiPON/LATP bi-layer,as shown in FIG. 1. The LiPON can be made by evaporating a LiPO₄ sourcein a plasma enhanced, nitrogen rich environment. The co-evaporation ofLiPO₄ and an Al₂O₃—TiO₂ source can create the LATP layer. Certainexemplary embodiments can create columnar ceramic microstructuresconsisting of highly textured, single crystal columns (these structuresare utilized as thermal barrier coatings for nickel based superalloycomponents in gas turbine engines). Following the bi-layer deposition,infiltration of a cyclo-olefin polymer or other non Li-ion conductingpolymer into the columnar pores will occur. A subsequent light gritblast or etching step (to expose the LATP surface) and dissolving thewater soluble NaCl layer can result in a free-standing separator.

Certain exemplary embodiments of UTPCC separator manufacture apply alithium ion conducting composite onto a flexible substrate materialfollowed by the eventual removal from the substrate prior to use. Thelithium ion conducting composite can have properties to survive shortterm exposure to a high temperature, oxidative environment. Based on theproperties of the ceramic materials (i.e. melting point) to beincorporated into the lithium ion conducting composite, a substratetemperature in the 300 to 700° C. range can be expected to create adesired columnar microstructure. Certain exemplary embodiments canutilize a thin, metal foil as the carrier material. Copper, stainlesssteel and/or nickel can provide high temperature capability andsufficient oxidation resistance (less so for copper) although othermetals or alloys could be utilized. Such metals can be dissolved usingacid solutions to provide a free standing UTPCC.

FIG. 1 shows A) a bi-layer LiPON/LATP deposition system and/or method1100; a UTCPP Separator 1200 in transportable form and; a UTCPPSeparator 1300 in final form. UTCPP Separator 1200 comprises acyclo-olefin polymer layer 1210, an LATP layer 1220, a LiPON layer 1230,and a metal foil layer 1240. UTCPP Separator 1300 comprises acyclo-olefin polymer layer 1310, an LATP layer 1320, and a LiPON layer1330.

FIG. 1 comprises:

-   -   ATV Technology 1000;    -   an atmosphere 1010;    -   a soft vacuum 1020;    -   a vacuum chamber wall 1030;    -   LiPON Deposition 1040;    -   a flexible substrate 1050;    -   LATP deposition 1110;    -   a vapor shield 1400;    -   3D Coating Technology 1600;    -   High Efficiency Deposition Technology 1700;    -   Multi-source Evaporation Technology 1800;    -   a first Al₂O₃/TiO₂ source 1810;    -   a first LiPO₄ source 1820;    -   a second Al₂O₃/TiO₂ source 1830;    -   a second LiPO₄ source 1840;    -   Ar carrier gas 1850;    -   a first nozzle 1860;    -   a third LiPO₄ source 1500;    -   Ar+N₂ carrier gas 1510;    -   a second nozzle 1520;    -   a cathode/anode 1900; and    -   a magnetically enhanced hollow cathode plasma with rapidly        switching cathode polarity 1910.

To meet a product cost target, the key techno-economic challenges are toobtain high deposition rates over large substrate areas usingcontinuous, roll-to-roll manufacturing. Certain exemplary embodimentsprovide a unique vapor deposition process that combines relatively highevaporation rates (using electron beam vaporization), relatively highdeposition efficiency (gas jet assist), relatively large area deposition(3D coating zone) and substantially continuous roll-to-rollmanufacturing (ATV technology) to enable high deposition rates (greaterthan approximately 10 microns/minute) over large areas (greater thanapproximately one m²) in a substantially continuous manner. Certainexemplary processes for UTPCC separator manufacture allows forsubstantially continuous manufacturing of certain processing steps.

FIG. 3 is a schematic representation of a system 3000, in whichelemental lithium metal is oxidized at an anode 3100 to form lithiumions 3020 and electrons 3040. Electrons 3040 flow through an electriccircuit 3700 across a load 3800 to do electric work, and lithium ions3020 migrate across an electrolyte 3500 to reduce oxygen (e.g., fromair) at a cathode 3600.

An electrolyte 3500 can be utilized to transport lithium ions 3020 toanode 3100, and can comprise solid-state lithium ion conductingmaterials, organic electrolytes, and/or aqueous electrolytes. Forexample, in an organic electrolyte, gaseous oxygen is reduced to formlithium peroxide at cathode 3600, and in aqueous solution reduction ofgaseous oxygen to lithium hydroxide occurs at cathode 3600. In certainexemplary embodiments, an ultra-thin polymer ceramic composite separator3400 can be used to resist water contact with anode 3100, and ultra-thinpolymer ceramic composite separator 3400 can be placed in closeproximity to anode 3100. Ultra-thin polymer ceramic composite separator3400 can comprise a first bi-layer 3200 and a second bi-layer 3300. Ifelectrolyte 3500 is organic the system 3000, ultra-thin polymer ceramiccomposite separator 3400 can be useful to keep oxygen and any introducedwater and CO₂ away from anode 3100. In certain exemplary embodiments,system 3000 can comprise a multi-electrolyte cell in which theelectrolyte solutions in contact with anode 3100 and cathode 3600 aredifferent.

Ultra-thin polymer ceramic composite separator 3400 can comprise abi-layer of Li-ion conducting ceramic materials, the bi-layer comprisingLiPON (e.g., first bi-layer 3200) and LATP (e.g., second bi-layer 3300),the bi-layer having a columnar grained microstructure. The columnargrained microstructure limits grain boundary resistance via alignment ofboundaries in a direction of Li-ion transport.

Ultra-thin polymer ceramic composite separator 3400 can be constructedfor use in system 3000 (e.g., which can comprise a battery). Ultra-thinpolymer ceramic composite separator 3400 can have a thickness of lessthan 20 micrometers. Ultra-thin polymer ceramic composite separator 3400can have a thickness of less than 10 micrometers.

Ultra-thin polymer ceramic composite separator 3400 can comprise aLi-ion conducting ceramic material. The Li-ion conducting ceramicmaterial can have having a columnar grained microstructure.

Ultra-thin polymer ceramic composite separator 3400 can comprise asingle or bi-layer combination of LiPON, LATP, garnets, lithiumsulfides, or Li_(1+2x)Zr_(2−z)Ca(PO₄)₃.

Ultra-thin polymer ceramic composite separator 3400 can comprise asingle or bi-layer combination of a glass, materials having a NASICONstructure, garnet, perovskite or sulfides having a thio-LISICONstructure (for example, Li_(3.25)Ge_(0.25)P_(0.75) S₄ or LGPS).

When system 3000 comprises a battery, the battery can be:

-   -   a lithium ion battery;    -   a lithium sulfur battery;    -   a lithium air battery; and/or    -   a solid state battery.

Ultra-thin polymer ceramic composite separator 3400 can comprise:

-   -   a non Li-ion conducting polymer; and/or    -   a cyclo-olefin and an ion-conducting ceramic.

The columnar grained microstructure can limit grain boundary resistanceby aligning grain boundaries in a direction of Li-ion transport.

FIG. 4 is a flowchart of an exemplary embodiment of a method 4000. Atactivity 4100, a sodium chloride layer can be deposited. At activity4200, a lithium layer can be deposited. For example, a lithium bi-layercan be deposited on a metal foil. The metal foil can have the sodiumchloride layer deposited thereon. An initial LiPON layer can bedeposited on the metal foil followed by an LATP layer. The bi-layer canbe deposited via a gas-jet assisted vapor deposition process thatoperates in a soft vacuum of approximately 10 Pa. The bi-layer can bedeposited via a gas-jet assisted vapor deposition process that utilizesnon-line-of-sight coating.

The bi-layer can comprise LiPON and/or LATP, wherein:

-   -   the LiPON portion of the bi-layer is deposited via evaporation        of a LiPO₄ source in a plasma enhanced, nitrogen rich        environment; and/or    -   the LATP portion of the bi-layer is deposited via co-evaporation        of LiPO₄ and Al₂O₃—TiO₂.

At activity 4300, a polymer can be infiltrated into the lithium layer.For example, a Li-ion conducting polymer can be infiltrated into thebi-layer. A non Li-ion conducting polymer can be infiltrated intocolumnar pores of the bi-layer.

At activity 4400, a surface of the lithium layer can be exposed. Forexample, the bi-layer can be etched to expose an LATP surface. In otherembodiments, the bi-layer can be grit blasted to expose an LATP surface

At activity 4500, the sodium chloride layer can be dissolved. Atactivity 4600, a substrate comprising the lithium layer can be etched toleave a free-standing ultra-thin polymer ceramic composite separator.

The bi-layer can comprise columnar ceramic microstructures, the columnarceramic microstructures comprising single crystal columns. The bi-layercan be deposited via a substantially continuous process.

Definitions

When the following terms are used substantively herein, the accompanyingdefinitions apply. These terms and definitions are presented withoutprejudice, and, consistent with the application, the right to redefinethese terms during the prosecution of this application or anyapplication claiming priority hereto is reserved. For the purpose ofinterpreting a claim of any patent that claims priority hereto, eachdefinition (or redefined term if an original definition was amendedduring the prosecution of that patent), functions as a clear andunambiguous disavowal of the subject matter outside of that definition.

a—at least one.

activity—an action, act, step, and/or process or portion thereof.

adapter—a device used to effect operative compatibility betweendifferent parts of one or more pieces of an apparatus or system.

align—to be arranged in substantially a straight line.

and/or—either in conjunction with or in alternative to.

apparatus—an appliance or device for a particular purpose

associate—to join, connect together, and/or relate.

battery—one or more electrochemical cells adapted to convert storedchemical energy into electrical energy.

bi-layer—a structure comprising two layers.

boundary—a border.

can—is capable of, in at least some embodiments.

circuit—an electrically conductive pathway and/or a communicationsconnection established across two or more switching devices comprised bya network and between corresponding end systems connected to, but notcomprised by the network.

columnar grained—having a structure that comprises crystals grown in asubstantially regular manner when a vertical section is viewed.

columnar pores—apertures defined in a columnar grained microstructure.

comprising—including but not limited to.

configure—to make suitable or fit for a specific use or situation.

connect—to join or fasten together.

constructed to—made to and/or designed to.

continuous process—a flow production method used to manufacture,produce, or process materials substantially without interruption.

convert—to transform, adapt, and/or change.

coupleable—capable of being joined, connected, and/or linked together.

coupling—linking in some fashion.

crystal column—a row of solid grains of a substance having acharacteristic internal structure and enclosed by symmetrically arrangedplane surfaces, intersecting at definite and characteristic angles.

cyclo-olefin—any of a homologous series of unsaturated, alicyclichydrocarbons, as cyclooctatetraene and cyclopentadiene, containing onedouble bond in the ring and having the general formula C₁₁H_(2n−2).

define—to establish the outline, form, or structure of.

deposit—to place something on a surface.

determine—to obtain, calculate, decide, deduce, and/or ascertain.

device—a machine, manufacture, and/or collection thereof.

direction—a line along which something moves.

dissolve—to mix with a liquid and become part of the liquid.

etch—to cut into something via a substance such as an acid.

evaporate—to change from a liquid or solid state into a vapor state.

expose—to remove a material from a covered surface.

garnet—any of several red, brown, black, green, or yellow mineralshaving the general chemical formula A₃B₂SiO₈, where A is either calcium(Ca), magnesium (Mg), iron (Fe), or manganese (Mn) and B is eitheraluminum (Al), manganese, iron, chromium (Cr), or vanadium (V). Garnetcrystals are dodecahedral in shape, transparent to semitransparent, andhave a vitreous luster. A garnet can be an LLZO garnet and/or cancomprise Li₇La₃Zr₂O₁₂.

gas turbine engine—a type of internal combustion engine that has anupstream rotating compressor coupled to a downstream turbine, and acombustion chamber or area, called a combustor, in between.

gas-jet assisted vapor deposition process—a method of coating a materialthat utilizes conveyance of a coating material via a stream of asubstance in a gaseous state.

generate—to create, produce, give rise to, and/or bring into existence.

glass—a substantially noncrystalline substance (e.g., comprising LiPON).

grain boundary resistance—an impedance to electrical conductivity causedby crystalline borders in a microstructure.

grit blast—to change a surface via particulates entrained in a gasstream.

infiltrate—to undergo or cause to undergo the process in which a fluidpasses into the pores or interstices of a solid.

install—to connect or set in position and prepare for use.

ion conducting ceramic—a substance that comprises a material such as,for example, silicon carbide, alumina, silicon carbide, zirconium oxide,and/or fused silica, calcium sulfate, luminescent optical ceramics,bio-ceramics, and/or plaster, etc. that is capable of transporting ionsbetween a battery anode and cathode.

LATP—Li_(1+x)Al_(x)Ti_(2−x)P₃O₁₂.

layer—a quantity of material placed on the surface of something.

LCZP—Li_(1+2x)Zr_(2−z)Ca(PO₄)₃.

Li-ion conducting ceramic material—a substance that comprises a materialsuch as, for example, silicon carbide, alumina, silicon carbide,zirconium oxide, and/or fused silica, calcium sulfate, luminescentoptical ceramics, bio-ceramics, and/or plaster, etc. that is capable oftransporting lithium ions between a battery anode and cathode.

Li-ion conducting polymer—a large molecule, or macromolecule, composedof many repeated subunits that is capable of transporting lithium ionsbetween a battery anode and cathode.

Li-ion transport—movement of lithium ions between a battery anode andcathode.

limit—to restrict something.

LiPON—lithium phosphorous oxy-nitride.

lithium sulfide—a substance that comprises a compound of lithium andsulfur with a more electropositive element or group of elements.

may—is allowed and/or permitted to, in at least some embodiments.

metal foil—a thin sheet of a material, the material is typically hard,opaque, shiny, and has good electrical and thermal conductivity. Metalsare generally malleable—that is, they can be hammered or pressedpermanently out of shape without breaking or cracking—as well as fusible(able to be fused or melted) and ductile (able to be drawn out into athin wire). About 91 of the 118 elements in the periodic table aremetals.

method—a process, procedure, and/or collection of related activities foraccomplishing something.

microstructure—the structure of a prepared surface of material asrevealed by a microscope above approximately 25× magnification.

NASICON structure—NASICON is an acronym for sodium (Na) Super IonicConductor, which refers to a family of solids with the chemical formulaNa₁+xZr₂SixP₃−xO₁₂, 0<x<3. A NASICON structure describes similarcompounds where Na, Zr and/or Si are replaced by isovalent elements.NASICON compounds have high ionic conductivities, on the order of 10-3S/cm, which rival those of liquid electrolytes. Substances having aNASICON structure can comprise, for example, Li₁+yAl_(y)Ti₂−y(PO₄)₃and/or LATP.

nitrogen rich environment—having a nitrogen concentration that isgreater than a nitrogen content of air (i.e., a nitrogen content greaterthan 79%).

non-line-of-site coating—placing a material on portions of somethingthat are not visible to a human via observation from a fixed point inspace from which the material enters a coating system.

particle diameter—an distance across a greatest extent of a particle.

perovskite—any material with the same type of crystal structure ascalcium titanium oxide (CaTiO₃), known as the perovskite structure, or^(XII)A^(2+VI)B⁴⁺X²⁻ ₃ with the oxygen in the face centers (such as, forexample, La_(0.51)Li_(0.34)TiO_(2.94)).

plasma—one of four main states of matter, similar to a gas, butconsisting of positively charged ions with most or all of their detachedelectrons moving freely about.

plasma enhanced—energized via a plasma generator.

plasma flux—a flow of plasma from a plasma source.

plasma generator—a system constructed to impart energy to a coatingmaterial and thereby generate a plasma.

plurality—the state of being plural and/or more than one.

predetermined—established in advance.

provide—to furnish, supply, give, and/or make available.

receive—to get as a signal, take, acquire, and/or obtain.

repeatedly—again and again; repetitively.

request—to express a desire for and/or ask for.

set—a related plurality.

single—substantially one.

substantially—to a great extent or degree.

superalloy—a mixture comprising a metal that exhibits: excellentmechanical strength, resistance to thermal creep deformation, goodsurface stability, and resistance to corrosion or oxidation.

support—to bear the weight of, especially from below.

system—a collection of mechanisms, devices, machines, articles ofmanufacture, processes, data, and/or instructions, the collectiondesigned to perform one or more specific functions.

thermal barrier coating—a surface covering that provides insulation fromheat transfer.

thickness—a distance measured between opposing surfaces of something.

thio-LISICON structure—LISICON is an acronym for Lithium Super IonicConductor, which refers to a family of solids with a chemical formulaLi_(2+2x)Zn_(1−x)GeO₄. A NASICON structure describes similar compounds.For example, Li_(3.25)Ge_(0.25)P_(0.75)S₄ or LGPS have a thio-LISICONstructure.

ultra-thin polymer ceramic composite separator—a layered structure thatis less than approximately 20 micrometers thick and positioned adjacentto a lithium battery anode.

utilize—to use something for a particular purpose.

via—by way of and/or utilizing.

Note

Still other substantially and specifically practical and usefulembodiments will become readily apparent to those skilled in this artfrom reading the above-recited and/or herein-included detaileddescription and/or drawings of certain exemplary embodiments. It shouldbe understood that numerous variations, modifications, and additionalembodiments are possible, and accordingly, all such variations,modifications, and embodiments are to be regarded as being within thescope of this application.

Thus, regardless of the content of any portion (e.g., title, field,background, summary, description, abstract, drawing figure, etc.) ofthis application, unless clearly specified to the contrary, such as viaexplicit definition, assertion, or argument, with respect to any claim,whether of this application and/or any claim of any application claimingpriority hereto, and whether originally presented or otherwise:

there is no requirement for the inclusion of any particular described orillustrated characteristic, function, activity, or element, anyparticular sequence of activities, or any particular interrelationshipof elements;

no characteristic, function, activity, or element is “essential”;

any elements can be integrated, segregated, and/or duplicated;

any activity can be repeated, any activity can be performed by multipleentities, and/or any activity can be performed in multiplejurisdictions; and

any activity or element can be specifically excluded, the sequence ofactivities can vary, and/or the interrelationship of elements can vary.

Moreover, when any number or range is described herein, unless clearlystated otherwise, that number or range is approximate. When any range isdescribed herein, unless clearly stated otherwise, that range includesall values therein and all subranges therein. For example, if a range of1 to 10 is described, that range includes all values therebetween, suchas for example, 1.1, 2.5, 3.335, 5, 6.179, 8.9999, etc., and includesall subranges therebetween, such as for example, 1 to 3.65, 2.8 to 8.14,1.93 to 9, etc.

When any claim element is followed by a drawing element number, thatdrawing element number is exemplary and non-limiting on claim scope. Noclaim of this application is intended to invoke paragraph six of 35 USC112 unless the precise phrase “means for” is followed by a gerund.

Any information in any material (e.g., a United States patent, UnitedStates patent application, book, article, etc.) that has beenincorporated by reference herein, is only incorporated by reference tothe extent that no conflict exists between such information and theother statements and drawings set forth herein. In the event of suchconflict, including a conflict that would render invalid any claimherein or seeking priority hereto, then any such conflicting informationin such material is specifically not incorporated by reference herein.

Accordingly, every portion (e.g., title, field, background, summary,description, abstract, drawing figure, etc.) of this application, otherthan the claims themselves, is to be regarded as illustrative in nature,and not as restrictive, and the scope of subject matter protected by anypatent that issues based on this application is defined only by theclaims of that patent.

What is claimed is:
 1. A system comprising: an ultra-thin polymer ceramic composite separator, the ultra-thin polymer ceramic composite separator comprising a bi-layer of Li-ion conducting ceramic materials, the bi-layer comprising LiPON and LATP, the bi-layer having a columnar grained microstructure.
 2. The system of claim 1, wherein: the columnar grained microstructure limits grain boundary resistance via alignment of boundaries in a direction of Li-ion transport.
 3. The system of claim 1, wherein: the ultra-thin polymer ceramic composite separator is constructed for use in a battery.
 4. The system of claim 1, wherein: the ultra-thin polymer ceramic composite separator has a thickness of less than 20 micrometers.
 5. The system of claim 1, wherein: the ultra-thin polymer ceramic composite separator has a thickness of less than 10 micrometers.
 6. A system comprising: a battery comprising an ultra-thin polymer ceramic composite separator, the ultra-thin polymer ceramic composite separator comprising a Li-ion conducting ceramic material, the Li-ion conducting ceramic material having a columnar grained microstructure.
 7. The system of claim 6, wherein: the ultra-thin polymer ceramic composite separator comprises a single or bi-layer combination of LiPON, LATP, garnets, lithium sulfides, or Li_(1+2x)Zr_(2−z)Ca(PO₄)₃.
 8. The system of claim 6, wherein: the ultra-thin polymer ceramic composite separator comprises a single or bi-layer combination of a glass, materials having a NASICON structure, garnet, perovskite or sulfides having a thio-LISICON structure.
 9. The system of claim 6, wherein: the battery is a lithium ion battery.
 10. The system of claim 6, wherein: the battery is a lithium sulfur battery.
 11. The system of claim 6, wherein: the battery is a lithium air battery.
 12. The system of claim 6, wherein: the battery is a solid state battery.
 13. The system of claim 6, wherein: the ultra-thin polymer ceramic composite separator has a thickness of less than 20 micrometers.
 14. The system of claim 6, wherein: the ultra-thin polymer ceramic composite separator comprises a non Li-ion conducting polymer.
 15. The system of claim 6, wherein: the ultra-thin polymer ceramic composite separator comprises a cyclo-olefin and an ion-conducting ceramic.
 16. The system of claim 6, wherein: the columnar grained microstructure limits grain boundary resistance by aligning grain boundaries in a direction of Li-ion transport.
 17. A method comprising: depositing a bi-layer on a metal foil, the metal foil having deposited sodium chloride thereon, the bi-layer comprising a LiPON and LATP, wherein: the LiPON portion of the bi-layer is deposited via evaporation of a LiPO₄ source in a plasma enhanced, nitrogen rich environment; and the LATP portion of the bi-layer is deposited via co-evaporation of LiPO₄ and Al₂O₃—TiO₂.
 18. The method of claim 17, further comprising: infiltrating a Li-ion conducting polymer into the bi-layer.
 19. The method of claim 17, further comprising: infiltrating a non Li-ion conducting polymer into columnar pores of the bi-layer.
 20. The method of claim 17, further comprising: etching the bi-layer to expose an LATP surface.
 21. The method of claim 17, further comprising: grit blasting the bi-layer to expose an LATP surface.
 22. The method of claim 17, further comprising: dissolving the deposited sodium chloride.
 23. The method of claim 17, further comprising: etching away a substrate comprising the bi-layer to leave a free-standing ultra-thin polymer ceramic composite separator.
 24. The method of claim 17, wherein: the bi-layer comprises columnar ceramic microstructures, the columnar ceramic microstructures comprising single crystal columns.
 25. The method of claim 17, wherein: the bi-layer is deposited via a substantially continuous process.
 26. The method of claim 17, wherein: an initial LiPON layer is deposited on the metal foil followed by an LATP layer.
 27. The method of claim 17, wherein: the bi-layer is deposited via a gas-jet assisted vapor deposition process that operates in a soft vacuum of approximately 10 Pa.
 28. The method of claim 17, wherein: the bi-layer is deposited via a gas-jet assisted vapor deposition process that utilizes non-line-of-sight coating. 